The study on the factors influencing sulfinatodehalogenation of perfluorohexyl chloride plus octene- 1 by using Na2S2O4/NaHCO3 discovered that among the various solvents tested (e.g. Me2SO, NMP, DMAc, CH3CN, CH3CN/H2O) at different temperatures, Me2SO was found to be the most suitable solvent and the conversion of the chloride was very dependent on the reaction temperature. When Me2SO was used in the reaction of perfluoroalkyl iodides, the reaction temperature could be decreased by 20degreesC as compared with that carried out in CH3CN/H2O to reach the comparable yields.